Phosphorodithiolates

ABSTRACT

METHOD FOR CONTROLLING INSECTS AND FUNGI, IN WHICH THE INSECTS AND FUNGI ARE CONTACTED WITH A PHOSPHOROIDITHIOLATE OF THE FORMULA   A-S-P(=O)(-OR)-S-B   WHEREIN R IS LOWER ALKYL: A IS A LOWER ALKYL ETC AND H IS PHENYLALKYL ETC. TWO TYPICAL EXAMPLES OF THE PHOSPHORODITHIOLATES ARE SHOWN BY THE FORMULA   (C2H5-S-P(=O)(-O-C4H9)-S-CH2-)-BENZENE   (C4H9-S-P(=O)(-O-C2H5)-S-CH2-)-BENZENE   THE COMPOUNDS CAN BE PREPARED BY CONDENSING A DITHIOATE OF THE FORMULA,   (A-S-P(=0)(-OR)=S)M   WHEREIN A AND R ARE AS MENTIONED ABOVE M IS AN ALKALI METAL OR AMMONIUM GROUP WITH A HALIDE OF THE FORMULA,   B.HAL   WEREIN B IS AS MENTIONED ABOVE AND HAL IS HALOGEN.

United States Patent 3,825,633 PHOSPHORODITHIOLATES Hiroshi Tsuchiya, Ashiya, Kunio Mukai, Nishinomiya, Akio Kimura, Takarazuka, Keimei Fujimoto, Kyoto, Toshiaki Ozaki and Sigeo Yamamoto, Toyonaka, Yositosi Okuno, Nishinomiya, Taizo Ogawa, Minoo, Toshiyuki Wakatsuki, Kyoto, and Yoshihiko Nishizawa, Nara, Japan, assignors to Sumitomo Chemical Company, Ltd., Osaka, Japan No Drawing. Application Aug. 5, 1970, Ser. No. 61,468, now Patent No. 3,725,546, which is a continuation-in. part of abandoned application Ser. No. 690,725, Dec. 15, 1967. Divided and this application Nov. 21, 1972, Ser. No. 308,585

Claims priority, application Japan, Dec. 20, 1966, 41/553,746; Feb. 18, 1967, 42/ 10,576; Mar. 10, 1967, 42/ 15,087

Int. Cl. A01n 9/36; C07f 9/16 U.S. Cl. 260-956 1 Claim ABSTRACT OF THE DISCLOSURE Method for controlling insects and fungi, in which the insects and fungi are contacted with a phosphorodithiolate of the formula,

wherein R is a lower alkyl; A is a lower alkyl, etc.; and B is phenylalkyl, etc. Two typical examples of the phosphorodithiolates are shown by the formula The compounds can be prepared by condensing a dithioate of the formula,

a-o s wherein A and R are as mentioned above M is an alkali metal or ammonium group, with a halide of the formula,

B-Hal wherein B is as mentioned above and Hal is halogen.

This application is a division of application Ser. No. 61,468, filed Aug. 5, 1970, now Pat. 3,725,546 which in turn is a continuation-in-part of application Ser. No. 690,725, filed Dec. 15, 1967, now abandoned.

The present invention relates to a novel use of phosphorodithiolates of the formula,

A-S1 -S-B wherein R is a C -C alkyl group, A is an alkyl group, a cycloalkyl group or a phenylalkyl group of the formula,

wherein D is an alkylene group, X is a hydrogen atom, a halogen atom, an alkyl group or a nitro group and n is an integer of 1 to 5, and B is an alkyl group, an alkenyl 3,825,633 Patented July 23, 1974 ice wherein D is an alkylene group and X and n have same meanings as defined above, provided that B is a phenylalkyl group when A is an alkyl group and that the total number of the carbon atoms of the alkylene groups of D and D is 3 or more when both A and B are the phenylalkyl groups.

At present, the application as agricultural chemicals of organo-mercuric compounds, which have been used in extremely large quantities, comes into serious problems due to their strong toxicity to men and cattle.

Hitherto, it is known that there are various kinds of organo-phosphorous compounds having either insecticidal activity or fungicidal activity. However, there has not been known any organo-phosphorous compound which has insecticidal activity as Well as fungicidal activity.

The present inventors made repeated studies to find chemicals which maintain strong activity against insects and fungi without toxicity to mammals. As a result, the present inventors have found phosphorodithiolates of the above-mentioned formula are excellent agricultural insecticide and fungicide.

One object of the present invention is to provide a novel insecticidal and fungicidal use of the phosphorodithiolates of the above-mentioned formula. Other objects of the present invention will be clear from the following description.

In order to accomplish these objects, the present invention provides a method for controlling insects and fungi, which comprises contacting the insects and fungi with a phosphorodithiolate of the above-mentioned formula.

According to the present invention, the compounds of the present invention have such broad and excellent biological eifects that they can control fungi simultaneously with injurious insects. In addition, they contain no such poisonous heavy metal as in the case of the organo-mercuric compounds and hence bring about a great advantage in handling.

The compounds of the present invention, which are represented by the formula as mentioned above, are ob tained by reacting dithioate represented by the formula,

wherein A and R are as mentioned before; and M is an sented by the formula,

B'Hal wherein B is as mentioned before; and Hal is a halogen atom.

Generally, the reaction of said dithioate with said halides is effected in the presence of organic solvents or Water as solvents. When there are used as solvents those which are relatively high in polarity such as water, alcohols, ketones and acetonitrile, favorable results are obtained. However, there are some cases where the desired compounds can be obtained in high yields even in the absence of solvent.

The reaction conditions vary depending on the kind of starting materials employed. Generally, however, the reaction temperature is from room temperature to about C., and the reaction time is from 1 hour to about 20 hours. If the starting materials employed are difficult to react, reaction accelerator, e.g. iodide, may be added, whereby the reaction rates can be accelerated and the yields can be 3 4 increased. After completion of the reaction, ordinary after- TABLE-Continued treatments are effected to obtain the desired compounds. (12)--.- S(C4HD-I1) The phosphorodithiolates of the above-mentioned formula in which R is a C -C alkyl; A is a phenylalkyl of E the formula, 5 S

wherein D, X and n are as defined above; and B is an alkenyl group, an alkynyl group or a haloalkyl group; (14% 0 swam-$09 are novel compounds, and those in which R is a C -C 021150-1 alkyl are preferable with respect to biological activity.

The dithiol phosphates obtained in the above manner may be practically used as such; but may further be pur1- 05L 0 S (08mm) fled according to column chromatography. Typical examples of the compounds of the present invention are as exemplified below, but compounds which SCHzare in accord with the object of the present invention are,

of course, not limited to these. 6) 0 s 02H;

H CzHsO-P 1) fi/SCZHB s H K s a la-n) 8 CH2 C2H50P (limo-P 0 S (Cilia-n) s CH1 C2H50-P TABLEComtlnued O S-CHa- S-CHnCHr- 8 TABLE-Continued 0 s-om@ ll CzH50P SCaH1(n) (mixture of orthoand para-forms):

7s ll l CzHsO-P CH:

SCsH7(n) 79 0 MMQ ll (1))CzH50-P SC3H7(n) The preparation of the compounds used in the present invention will be illustrated below with reference to examples. But it is not needed to say that the present invention is not limited to them.

EXAMPLE 1 To a solution comprising 12.6 g. of potassium O-ethyl- S-n-butyl phosphorodithioate and 50 m1. of water, 6.4 g. of benzyl chloride was added dropwise with stirring at 50 C. The mixture was reacted at C. for 4 hours. Thereafter, the reaction liquid was extracted with toluene and was washed with a 5% aqueous sodium carbonate solution and then with water, and the toluene layer was dried with anhydrous Glaubers salt. Subsequently, toluene was removed by distillation to obtain a light yellow oily substance which was O-ethyl-S-n-bntyl-S-benzyl phosphorodithiolate, yield 89%. This substance was subjected to column chromatography using active alumina. The refractive index of the thus treated substance was n 1.5510, and the elementary analysis values thereof were as follows:

Found (percent): P, 10.19; S, 21.11. Calculated (percent): P, 10.17; S, 21.07.

EXAMPLE 2 To a solution comprising 15.0 g. of potassium O-ethyl- S-a-phenylethyl phosphorodithioate and 50 ml. of acetone, 6.7 g. of n-propylbromide was added dropwise with stirring at 50 C., and the mixture was refluxed for 4 hours. The deposited potassium bromide was separated by filtration and acetone was removed by distillation. The residual oily substance was dissolved in toluene and was subjected to the same treatment as in Example 1 to obtain a light yellow oily substance which was O-ethyl-S-n-propyl S-aphenylethyl phosphorodithiolate, yield 77%. This substance was subjected to column chromatography using active alumina. The refractive index of the thus treated substance was 11 1.5496, and the elementary analysis values thereof were as follows:

Found (percent): P, 9.73; S, 20.61. Calculated (percent): P, 10.17; S, 21.06.

EXAMPLE 3 To a solution comprising 14.2 g. of sodium 1-ethyl-S-2- phenylethyl phosphorodithioate and 50 ml. of water, 6.3 g. of benzyl chloride was added dropwise at 50 C. over a period of about 1 hour, and the mixture was reacted with stirring at C. for 3 hours. Subsequently, the reaction liquid was subjected to the same treatments as in Example 1 to obtain a light yellow oily substance which was 0- ethyl S 2 phenylethyl S benzyl phosphorodithiolate, yield 92%. The refractive index of the substance was 11 1.5834, and the elementary analysis values thereof were as follows:

Found (percent): P, 8.77; S, 18.30. Calculated (percent): P, 8.81; S, 18.18.

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Further, the present compounds may be used in admixture with other chemicals to broaden the applicable scope thereof. For example, they may be used in admixture with organo-chlorine type fungicides such as pentachlorobenzyl alcohol and the like, organo-arsenic type fungicides such as iron methylarsonate and the like, organo-sulfur type fungicides, or antibiotics. In addition thereto, they may be used in admixture with organo-chlorine type, organo-phosphorus type, pyrethroid type or carbamate type insecticides such as 'y-1,2,3,4,5,6-hexachlorocyclohexane,

1, 1, 1-trichloro-2,2-bis( p-chlorophenyl ethane,

0,0-dimethyl-O-(p-nitrophenyl) phosphorothioate,

S'[1,2-bis(ethoxycarbonyl)ethyl] 0,0-dimethyl phosphorodithioate,

0,0-dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate,

O-ethyl O-p-nitrophenyl phenylphosphonothiorate,

u-naphthyl N-methyl carbamate,

0,0-dimethyl-O-(p-nitro-m-methylphenyl) phosphorothioate,

3,4,5, 6tetrahydrophthalimidemethyl chrysanthemate, and

3,4-dimethylphenyl N-methyl carbamate,

and further with the above-mentioned fungicides. Further, they may be used in admixture with agricultural chemicals such as herbicides, e.g. 2,4-dichlorophenoxyacetic acid, 4- chloro-Z-methylphenoxyacetic acid, 3,4-dichloropropionanilide, nematocides or miticides, or with fertilizers. A synergistic effect due to mixing can be expected depending on combinations with said chemicals.

The present invention will be illustrated in further detail below with reference to examples, but the kinds and mixing proportions of compounds and additives are not limited only to those shown in the examples but are variable within wide ranges. In Examples 69-96, the compounds are referred to number of the above mentioned typical compounds. All parts are based on weight.

EXAMPLE 69 Dust 3 parts of compound (2) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3% of active ingredient. In application, the dust is dusted as such.

EXAMPLE 70 Dust 4 parts of compound (73) and 96 parts of a clay-talc mixture are thoroughly pulverized and mixed together to obtain a dust containing 4% of active ingredient. In application, the dust may be used either as such or in thorough admixture with a soil.

EXAMPLE 71 Wettable powder 50 parts of compound (7), parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly pulverized and mixed together to obtain a Wettable powder containing 50% of active ingredient. In application, the powder is diluted with water and is then sprayed.

18 EXAMPLE 72 Emulsifiable concentrate 50 parts of compound (9), 20 parts of xylene and 30 parts of the emulsifier Sorpol 2020 (registered trade name) (polyoxyethylene phenyl phenol polymer type) are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50%. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 73 Emulsifiable concentrate Oil preparation 1 part of compound (1) and '99 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of 1%. In application, the preparation is atomized or sprayed as such or is poured into a hole bored in a soil.

EXAMPLE 75 Granules 5 parts of compound (3), 93.5 parts of clay and 1.5 parts of Gohsenol (polyvinyl alcohol) registered trade name) are thoroughly kneaded with water, and the mixture is granulated and is then dried to obtain granules containing 5% of active ingredient. In application, the preparation is applied as such.

EXAMPLE 76 Dust 3 parts of compound (40) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3% of active ingredient. In application, the dust is dusted as such.

EXAMPLE 77 Dust 1.5 parts of compound (22) and 98.5 parts of a claytalc mixture are thoroughly pulverized and mixed together to obtain a dust containing 1.5% of active ingredient. In application, the dust may be dusted as such or may be used in thorough admixture with a soil.

EXAMPLE 78 Wettable powder 50 parts of compound (27), 5 parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly pulverized and mixed together to obtain a Wettable powder containing 50% of active ingredient.

EXAMPLE 79 Emulsifiable concentrate 50 parts of compound (32), 20 parts of an emulsifier (polyoxyethylene alkylphenol ether type) and 30 parts of acetonitrile are mixed together to obtain an emulisifiable concentrate having an active ingredient concentration of 50%. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 80 Emulsifiable concentrate 40 parts of compound (33), 20 parts of an emulsifier (polyoxyethylene alkylphenol ether type) and 40 parts of xylene are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 40%. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 81 Oil preparation 1 part of compound (30), and 99 parts of purified kero sene are mixed together to obtain an oil preparation having an active ingredient concentration of 1%. In application, the preparation is atomized or sprayed as such.

EXAMPLE 82 Granules parts of compound (5), 90 parts of silica powder, 4.95 parts of calcium lignosulfonate and 0.05 part of sodium alkylbenzenesulfonate are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 5% of active ingredient. In application,

the preparation is sprinkled as such.

EXAMPLE 83 Dust 3 parts of compound (45) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3% or active ingredient. In application, the dust is dusted as such.

EXAMPLE 84 Dust 2 parts of compound (50) and 98 parts of a clay-talc mixture are thoroughly pulverized and mixed together to obtain a dust containing 4% of active ingredient. In application, the dust may be dusted as such or may be used in thorough admixture with a soil.

EXAMPLE 85 Wettable powder Emulsifiable concentrate 50 parts of compound (46), 35 parts of xylene and 15 parts of an emulsifier (polyoxyethylene alkylphenol ether type) are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50%. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 87 Emulsifiable concentrate 40 parts of compound (49), 40 parts of acetonitrile and 20 parts of an emulsifier (polyoxyethylene alkylphenol ether type) are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 40%. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 88 Oil preparation 0.5 part of compound (48) and 99.5 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of 0.5%. In application, the preparation is atomized or sprayed as such.

EXAMPLE 89 Granules 5 parts of compound (52), 90 parts of silica powder, 4.95 parts of calcium lignosulfonate and 0.05 part of so- 20 dium alkylbenzenesulfonate are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 5% of active ingredient. In application, the preparation is sprinkled as such.

EXAMPLE Dust 3 parts of compound (57) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust containing 3% of active ingredient. In application, the dust is dusted as such.

EXAMPLE 91 Wettable powder 50 parts of compound (59), 5 parts of wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly pulverized and mixed together to obtain a Wettable powder containing 50% of active ingredient. In application, the powder is diluted with water and sprayed.

EXAMPLE 92 Emulsifiable concentrate 50 parts of compound (53), 35 parts of xylene and 15 parts of an emulsifier (polyoxyethylene alkylphenol ether type) are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50%. In application, the concentrate is diluted with water and is then sprayed.

EXAMPLE 93 Oil preparation 0.5 part of compound (55) and 99.5 parts of purified kerosene are mixed together to obtain an oil preparation having an active ingredient concentration of 0.5%. In application, the preparation is atomized or sprayed as such.

EXAMPLE 94 Granules 5 parts of compound (61), 90 parts of silica powder, 4.95 parts of calcium lignosulfonate and 0.05 part of sodium alkylbenzenesulfonate are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 5% of active ingredient. In application, the preparation is sprinkled as such.

EXAMPLE 95 Emulsifiable concentrate 50 parts of compound (69), 30 parts of an emulsifier (polyoxyethylene alkylphenol ether type) and 20 parts of xylene are mixed together to obtain an emulsifiable concentrate having an active ingredient concentration of 50%. In application, the concentrate is diluted with water and is sprayed.

EXAMPLE 9'6 Granules 3 parts of compound (72), 95 parts of clay and 2 parts of Gohsenol (polyvinyl alcohol) (trade name for a product of Nippon Gosei Chemical Co., Ltd.) are thoroughly pulverized and mixed together. The mixture is kneaded with water, is granulated and is then dried to obtain a granular preparation containing 3% of active ingredient. In application, the preparation is sprinkled as such.

In order to substantiate the excellent preventive and extreminative effects of the present compounds, typical test results will be shown below. In Tables of the following Test Examples, the compounds are referred to by the numbers of the above-mentioned typical compounds.

21 user EXAMPLE 1 Test of control of rice blast In a 9 cm. in diameter flower pot, a rice plant (variety: Waseasahi) was cultivated to the 3-4 leavesstage. To the rice plant, each 100 mg. per pot of the present composition in the form of dusts were individually dusted by use of a bell jar duster. After 1 day, the rice plant was sprayed and inoculated with a spore-suspension of rice blast fungi (Pyricularia oryzae). 4 days thereafter, the number of spots generated was counted to investigate the fungicidal affects of individual compositions. The results are as shown in Table 2.

TABLE 2 Active ingredient concentration Preventive (percent) value Compound:

(1) V 3 100 (5) 3 97. 3 (7) 3 100 (9) 3 100 (10) 3 98. 9 (l3) 3 100 (18)-- 3 96. 8 (20) 3 95. 7 Phenylmercuric acetate dust 0. 42 98. 1

El) 3 48. 9 (CH3 SMPO CH! CH: S 0 3 57. 3

CHaO S-CHzCN Non-treatment- 0 TEST EXAMPIJE 2 Test of curative effects on rice blast In a 9 cm. in diameter flower pot, a rice plant (variety: Waseasahi) was cultivated to the 3 leaves stage. The rice plant was sprayed and inoculated with a spore-suspension of rice blast fungi (Pyricularia oryzae). After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 7 ml. per pot. 3 days thereafter, the number of spot generated was counted to investigate the fungicidal effects of individual compounds. The results are as shown in Table 3.

In Tables 2 and 3, the preventive and curative values indicate numeral values calculated according to the following equation:

Preventive (curative) value Test on the control of rice sheath blight A rice plant (variety: Kinnanpu) was cultivated in a porcelain pot. When the rice plant had grown to a height of about 50 cm., disk inoculum (5 mm. in diameter) of the mycelium of Pellicularia sasakii was inoculated onto the leaf sheaths of the rice plant. After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 10 ml. per pot. 5 days thereafter, the number of affected leaf sheaths was counted to obtain the results as shown in Table 4.

TEST EXAMPLE 4 A rice seedling (variety: Waseasahi) at the 3-4 leaves stage, which had elapsed 30 days after sowing, was immersed for 1 minute in an emulsion prepared by individually diluting with water to a given concentration the present compounds in the form of emulsifiable concentrates. After air-drying, the rice seedling was placed in a large size test tube. Subsequently, 30 adults of small brown planthopper (Delphaoodes striatellus Failn) were liberated in said test tube. After 24 hours, the number of killed insects was calculated, and the values of IE were calculated from the mortality. The results are as shown in Table 5.

TEST EXAMPLE 5 A mottled kideny bean plant at the 2 leaves stage, which had elapsed 20 days after sowing in a 9 cm. flower pot, was parasitizecl with a large number of two-spotted red spider mite (Tetranychus telarius Linn). The present compounds in the form of wettable powders were individually diluted with water to a given concentration, and the solution was sprayed in a proportion of 10 ml. per pot to the mottled kidney bean plant on a turn table. After 48 hours, the alive and dead of the red spider mite were observed to calculate the mortality thereof. The

results are as shown in Table 6.

TABLE 6 Active ingredient concentration (times) Mortahty Compound:

TEST EXAMPLE 6 TABLE 7 Number of Control survival value insects (percent)* Compound:

(7) 3 99. 9 (8) 5 99. 9 Non-treatment... 2, 530

Number of survival insects in non-treated area C ontrol- X100 value (percent) Number of Number of survival survival insects in noninsects in treated area treated area TEST EXAMPLE 7 Test of preventive effects on rice blast In a 9 cm. flower pot, a rice plant (variety: Waseasahi) was cultivated to the 3-4 leaves stage. To the rice plant, the present compounds in the form of dusts were individually dusted in a proportion of 100 mg. per pot by use of a bell jar duster. After 1 day, the rice plant was sprayed and inoculated with a spore-suspension of rice blast fungi (Pyrzcularia oryzae). 4 days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. The results are as shown in Table 8.

TABLE 8 Active ingredient concen- Preventration tive (percent) value 3 i 3.0 27.1 (CHgOhP-S-CH -Q-CHZSP 0 CH3):

Non-treatment 0 24 TEST EXAMPLE 8 Test of curature effects on rice blast A rice plant (variety: Waseasahi), which had been cultivated to the 3 leaves stage in a 9 cm. flower pot, was sprayed and inoculated with a spore-suspension of rice blast fungi (Pyricularia oryzae). After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed in a proportion of 7 ml. per pot. 3 days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. The results are as shown in Table 9.

TAB LE 9 I Active ingredient concentration Curative (p.p.m.) value Compound:

(2 500 97. 4 500 98. 6 500 500 99. 3 500 97. 2 500 98. 0 500 97. 6 500 100 500 100 500 99. 7 500 97. 4 500 95. 6 500 98. 8 500 97. 4 Control 0,0-diethyl-S-benzyl phosphorothioate- 500 73. 6 Control phenylmercuric acetate 30 48. 2

H 500 9. 1 n-olmsnroong H 500 7. 2 (CH SMP OCH;

N oil-treatment. 0

TEST EXAMPLE 9 Test on the control of rice sheath blight A rice plant (variety: Kinnanpu) was cultivated in a porcelain pot. When the rice plant had grown to a height of about 50 cm., a disk inoculum (5 mm. in diameter) of the mycelium of Pellicularia sasakii was inoculated onto the leaf sheaths of the rice plant. After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 10 ml. per pot. 5 days thereafter, the number of affected leaf sheaths was counted to obtain the results as shown in Table 10.

TABLE 10 Active Ratio of ingredient afiected concenleaf tration sheaths (p.p.m.) (percent) Compound:

1, 000 8. 7 1, 000 13. 2 1, 000 11. 1 (41 1,000 33. 5 Non-treatment 100 TEST EXAMPLE 10 (I) Test of efi'ects on smaller brown planthoppers (II) Test of effects on two-spotted red spider mite (Tetranvchus telarius Linn) A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of red spider adults. The plant was immersed for 1 minute in each of given concentration liquids of the present compounds in the form of wettable powders. After 48 hours, the mortality of insects at given concentrations were measured, and the values of LC were calculated from said mortality. The results are as shown in Table 11.

TEST EXAMPLE 11 Test of preventive effects on rice blast A rice plant (variety: Waseasahi) was cultivated in a 9 cm. flower pot to the 3-4 leaves stage. To the rice plant, the present compounds in the form of dusts were individually dusted by use of a bell jar duster in a proportion of 100 mg. per pot. After 1 day, the rice plant was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. 4 days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds, whereby each of the present compounds showed a preventive effect comparable to that of the control phenylmercuric acetate, as set forth in Table 12.

l Compound disclosed in Japanese Patent Publication 15,600/66.

TEST EXAMPLE 12 Test of curative effects on rice blast Arice plant (variety: Waseasahi), which had been cultivated in a 9 cm. flower pot to the 3 leaves stage, was sprayed and inoculated with a spore-suspension of Pyricularia oryzea. After 1 day, the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the rice plant in a proportion of 7 ml. per pot. 4 days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds, whereby the present compounds showed far more excellent curative effects than those of commercially available mercury preparation, organo phosphorus fungicide and the like, as set forth in Table 13.

TABLE 13 Compound:

100 100 90. 4 100 94. 6 100 95. l (4 100 100 Control 0,0-diethy1-S-benzyl-phosphorothio- 500 93. 2 ate 1 100 72. 8 Control O-ethyl-3-4-ehloro-Lnaphthylmethyl-S- Z-eyanobenzyl-dithiophosphate 2 100 49. 6 Control phenylmercuric acetate 30 64. 7

H 100 5. 6 (CHaS)2P 0 CH3 (1? 100 7. 1 (n-C HnS)zP-O N on-treatment. 0

1 Commercially available compounds. 2 Compound disclosed in Japanese Patent Publication 15,600/66.

TEST EXAMPLE 13 Test of the control of rice sheath blight A rice plant (variety: Kinnampu) was cultivated in a porcelain pot. When the plant had grown to a height of about 60 cm., the present compounds in the form of emulsifiable concentrates were diluted with water and were individually sprayed to the plant in a proportion of 10 ml. per pot. After 2 hours, a disk inoculum (5 mm. in diameter) of the mycelium of Pellicularia sasakii was inoculated on the leaf sheaths of the plant. 5 days thereafter, the number of affected leaf sheaths was counted to obtain the results as shown in Table 14.

TABLE 14 Ratio of affected leaf sheaths (percent) TEST EXAMPLE 14 Test of effects on tow-spotted red spider mite (Tetranychus telarius Linn) A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of adults of Tetranychus telarius. The leaves of said plant parasitized with the red spider mite were immersed for 1 minute in each of aqueous solutions of the present compounds in the form of wettable powders. After 48 hours, the alive and dead of the insects were observed to calculate L0 thereof. The results are as shown in Table 15.

TABLE 15 28 TEST EXAMPLE 15 TABLE 18 Active Well water was charged in a 500 cc. beaker. Into the ggggt Number beaker, full grown larvae of northern house mosquitoes nation ofspots were liberated, and then the present compounds in the P-P- Perleat form of granules were individually charged. After 24 Compound; hours, the alive and dead of the mosquito larvae were 3.3 observed to calulate the mortality thereof. The results are (55) as shown in Table 16. 3.3 3.3 TABLE 16 gg 1;; 62 a0 2.2 zzrg L050 (p 5 Pher 1yl mercurie acetate 0. 29 1. 8 (4 0.12 H 3.0 15.6 gig (CHaS)2POCHa 0 6 Non-treatment. 3-8

8%; TEST EXAMPLE 18 20 Test of effect on tow-spotted spider mite TEST EXAMPLE 16 A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing was parasitized Test of eul'atlve effects on nee blast with a large number of adults of Tetranychus lelarius 1 nt variet Waseasahi which had been Linne. The leaves of said plant parasit zed with said spider g gizf 5 2 figwer pot to the leaves stage, was 25 mites were immersed for 1 minute n each of aqueous sprayed and incubated with a spore suspnsion f solutions of the present compounds in the form of wet- Pyricularia myzae- After 1 day, the present compounds table powders. After 48 hours, the alive and dead of the in the form of emulsifiable concentrates were diluted with e 'SPlder were Observed tofaleulele the mortamy there water and were individually sprayed to the plant in a The results are as Shownm Table proportion of 7 ml. per pot. 4 days thereafter, the number TABLE p of spots generated was counted to investigate the fungicompound: LCEO (times) cidal effects of individual compounds. The res l s ar as (55) 5110,00) set forth in Table 17, and the present Omp01mdS Sh0W@d 57 2 0 000 markedly excellent curative elfects as compared with con- .(58) 3,000,000 trol compounds. 59) 900,000

TABLE 17 Control dimethoate (commercially avail- Actm able compound) Q50,0O0 ingredient Control O-ethyl-S,S-diphenyl phosphorogggfg; 5 32; dithiolate (known compound) 10,000 (p.p.m.) per leaf 0 d TEST EXAMPLE 19 11 Z 28g 0 g Test of insecticidal effects on adzuki bean weevil (2g; 2% {3 About 30 adults of Callosobruchus chinensis Linn were liberated in a styrol-made tube of 2 cm. in diameter 0 CN 500 and 7 cm. in length. Both ends of the tube were corked H with polyethylene film-covered corks. 'Into the tube, aqueous emulsions of the present compounds in the form of emulsifiable concentrates were individually charged, and the insects were immersed therein for 1 minute. Subsequently, the insects were taken out on a filter paper and (known command) were then transferred to a dish for observation. After ,3,0 0 500 11.8 24 hours, the alive and dead of the insects were observed \{L Q to calculate the mortality thereof. The results are as C H shown in Table 20.

TABLE 20 (Commercially available compound) LC Non-treatment- (times) 60 Compound:

(53) 34,000 (57) 66,000 TEST EXAM PLE 17 %8 Test of preventive effects on rice blast (e2) 010 Control O- ethyl-S,S-drphenylphosphorod1tblolate 1 250 T0 a rice Plant w Waseasahih, which had been 8332i5353322 13131::::::::::::::::::::::::':'"':::" 53'338 cultivated in a 9 cm. flower pot to the 3-4 leaves stage, C the present compounds in the form of dusts were dusted CH3S\ 2 200 in a proportion of 1-00 mg. per pot by use of a bell jar P duster. After 1 day, the plant was sprayed and inoculated cnao/ with a spore-suspension of Pyriculwria oryzae, 5 days thereafter, the number of spots generated was counted control 600 to investigate the fungicidal elfects of individual compounds. The results are as set forth in Table 18, and the present compounds were comparable in preventive effect to the control phenylmercuric acetate.

1 Known compound. I Commercially available compound.

29 TEST EXAMlIJE 20 Test of preventive efiects on rice blast' TABLE 21 Active ingredient concentration (percent) Preventive value PheEyImEGHh'tHtB'I:IIIIIIIIIII: Non-frmit-m nnf TEST EXAMPLE 21 Test of curative effects on rice blast A rice plant (variety: Waseasahi) was cultivated in a 9 cm. flower pot to the 3 leaves stage. The rice plant was sprayed and inoculated with a spore-suspension of Pyricularia oryzae. After 1 day, given concentration liquids of test compounds were individually sprayed to the plant in a proportion of 7 ml. per pot. 3 days thereafter, the number of spots generated was counted to investigate the fungicidal effects of the compounds. The results are as shown in Table 22.

TABLE 22 Curative value Compound:

Phenylmereuric acetate N on-treatment.

TEST EXAMPLE 22 In a porcelain Wagner pot, a pea plant was grown to a height of 20 cm. The plant was parasitized with a large number of adults of Tetranychus telarius Linn. Subse quently, 0.02% solution of the emulsifiable concentrate of Example 95 shown before was applied to the root portion of said plant in a proportion of 20 cc. per pot. When observed after days, all the red spider had been killed.

TEST EXAMPLE 23 Test of preventive effects on rice blast The procedure of Test Example 21 was repeated except that the following compounds were used instead of the compounds (63) and (64). The results are shown in Table 23.

TABLE 23 Active ingredient concentration (percent) Preventive value OOOOOOOOQQ a: coofisa Non-treatment 30 TEST EXAMPLE 24 Effect of controlling powdery mildew of cucurbitaceous plants Pumpkin plants (variety: Heiankogiku) were cultivated in the flower pots of 12 cm. in diameter. When the plant had grown to the 3-4 leaves stage, they were individually sprayed with 7 ml./pot of each of given concentration solutions of test chemicals in the form of wettable powers. One day after, the pumpkin seedlings were sprayed in inoculate with a spore-suspension of cucurbitaceous plant powdery mildew fungi (Sphaerotheca fuliginea). 10 days thereafter, the state of disease of 4 leaves at the upper portion of each. plant was observed and the diseased degree of the plant was calculated from the area of diseased spots generated.

In each treatment, 7 pots were tested to obtain the result shown in Table 24 below. As seen in the table, the present compounds showed markedly excellent controlling effects as compared with that of the conventional fungicide, sulfur.

TABLE 24 Degree of damage 2, 500 N on-treatment l Commercially available fungicide for controlling the powdery mildew TEST EXAMPLE 25 The procedure of Test Example 14 was repeated substituting the following compounds for the compounds used in said Example. The results are shown in Table 25.

The procedure of Test Example 15 was repeated substltuting the following compounds for the compounds used in said Example. The results are shown in Table 26.

TABLE 26 pound: Lc (p.p.m.) 0.066 0.03 0.03 0.016 0.011 0.027 (73) 0.005 0.062 0.022

31 TEST EXAMPLE 27 The procedure of Test Example 19 was repeated substituting the following compounds for the compounds used in said Example. The results are shown in Table 27.

What we claim is: 1. Novel phosphorodithiolates of the formula,

32 wherein R is a C -C alkyl, A is a phenylalkyl group of the formula,

wherein D is C -C alkylene, X is hydrogen, n is an integer of 1-5 and B is C -C alkenyl, propar'gyl or chlorinated C -C alkyl.

References Cited UNITED STATES PATENTS 3,716,580 1/1973 Kishino et a1 260-963 ANTON H. SUITO, Primary Examiner US. Cl. X.R. 

